Manufacture of azo dyestuffs



tained may be formula Patented May 19, 1931 UNITED STATES PATENT OFFICE RAINALD BRIG-HTMAN, OF BLAGKLEY, MANCHESTER, ENGLAND, ASSIGNOR TO IM- PERIAL CHEMICAL INDUSTRIES LIMITED, OFWESTMINSTEB, ENGLAND MANUFACTURE OF .AZO DYESTUFFS No Drawing. Application filed February 12, 1930,,Seria1 No. 427,960, and in Great Britain February phide-4-oxamic acid of the general formula ooonoorzO-a-O-rsm wherein n represents 1 or 3 with'one molecular proportion of a coupling component of such nature that the intermediate dyestulf thus obtained'is capable of further combination with a component. It is immaterial how this further combination is effected. It may for instance be effected by providing that the intermediate dyestuif contains a further diazotizable amino group which is treated with nitrite and acid and coupled up with a further component or the intermediate dyestuif may be of such a nature that it is capable of combination with a further molecular proportion of a diazo compound with which it is caused to couple. The dyestufis thus obrepresented by the general in which Y represents the residue of an oXamic acid derivative of the formula given above. X represents the divalent residue of an intermediate coupling component and Z the coupled residue of an azo dye component. By the term coupled residue of an azo dye component I mean the coupled residue from an azo dye coupling component or from a diazotized coupling component.

The dyestuffs obtained maybe used for v H V I V, wherein n represents 1 or 3; a diaminated body of the formula X('NH and an aminated compound of the formula Z (NH it The less soluble ones are espebeing understood that nitro groups in the original body will be reduced 'to' amino groups. 1 y My invention is illustrated but not limited by the following examples, in which the parts are by weight.

Ewample 1.-The suspension of diazo coma pound obtained from 352 parts of 4t-aminodiphenyltrisulphide--oxamic. acid as described in Example 5 is stirred into .a solution of 112 parts of m-phenylenediamine containing 600 parts ofsodium carbonate. The mixture is stirreduntil coupling is complete, when there is run into it a solution of p-chlo'robenzene diazonium chloride obtained by di-f azotizing 127.5 partsof p-chloro-aniline-with 250 parts of 36 per cent hydrochloric acid and 69 parts of sodiumnitrite in the usual Way. The mixture is maintained alkaline by the addition of further sodium carbonate if required and is stirred until coupling is complete when it is heated up and the dyestuff isolated by the addition of common salt. It dyes cellulose acetate rayon anorange-brown shade. I a I If the m-phenylenediamine is first combined with the diazotized oxamic acid de rivative of thioaniline' and finally with idlazoti'zed p-nitroaniline atdye is obtained which dyes acetate rayonreddish brown.

Ewample 2.The suspension of diazo compound'obtained from 288 parts of l-aminodiphenyl-sulphide--oxamic acid is stirred into a solution of 126 parts of m-toluylenedi amine containing 400 parts of sodium carbonate. The mixture is stirred until coupling iscomplete when it is run into a solution containing 188 parts of 2 -dinitroaniline diazotized in the known manner. The mixture is stirred untilcoupling is complete,'when it-is made neutral, heated up and the dyestulf 'filtered ofi. It dyes cellulose acetate rayon a warm I brown shade. form of its freer acid is probably represented This'dyestufi in the.

amine and Y represents the coupled residue of an oxamic acid derivative of the formula:

oooncogO-m-O-nm wherein n represents 1 or 3; the steps which comprise coupling a diazotized oxamic acid derivative of the above formula with an intermediate coupling component and further coupling the resulting product with said diazotized amine.

3. In the process of manufacturing new azo Colour on acetate rayon Lgggnodiphenyltrisulphide 4'-oxamic )Meta phenylene diqmim 4-aminodiphenyl-sulphide-pxamic acid.

Meta-toluylene diamine Orange brown. Orange ye1low.

p-Am.ino-sallcylic-acid hp-nnisidine 4-aminodiphenyl-sulphide-4-oxamic acid. 1:5-arnino-naphthol 2:5-dich1oroaniline Bluish pink.

(Coupled alkaline) (Coupled acid.)

Colour on wool 4-aminndiphenyl-sulphide 4-oxamic acid. m-phenylene diamine Sulphanilic acid Orange brown.

4-aminodiphenyl-sulphide 4-oxan1ic acid- Resorcinol 216-naptl1ylamine-sulphonic acid Orange brown; 'kaminodiphenyl-sulphide 4-oxamic acid. Crcsirline 01 Yellow brown. 4-eminodiphenyl-sulphide 4-oxamic acid. Cresidine Reddish brown 4-aminodiphenyl-sulphide 4-o :amic acid. a-naphthyla Orange brown. 4-aminodipheny1-sulphide 4-oxamic acid Cleves acid. Brown.

phonic acid.

Colour on cotton and viscose rayon L-aminodiphenyl-trisulphide -4- oxamic Cresidine *2 phenylamino 5 naphthol 7- sul- Violelt t and red acid.

phonic acid.

Having now particularly described and ascertained the nature of my said invention and in what manner the same is to be performed, I declare that what I claim is 1. In the process of manufacturing new azo dyestuffs suitable for dyeing wool, acetate rayon, viscose rayon and cotton and which may be represented by the probable formula:

Y-N=NXN=NZ wherein X represents the divalent residue of an intermediate coupling component, Z the coupled residue of an azo dye component, and Y represents the coupled residue of an oxamic acid derivative of the formula:

in which X represents the divalent residue of an intermediate coupling component, Z represents the coupled residue of a diazotized dyestuffs suitable for dyeing acetate rayon and wool and represented by the probable formula and wool and represented by the probable formula oooncoay-O-s-O-mn wherein R represents hydrogen or CH and Z the monovalent residue of a diazotized amino body; the steps which comprise coupling a diazotized 4-aminodiphenylsulphideA- oXamic acid with a metadiamine and causing the intermediate dyestuff thus obtained to combine with a diazotized coupling component.

1 5. In the process of manufacturing new azo dyestuffs suitable for dyeing acetate rayon and wool and represented by the probable formula COOH.CO.N S N=N N=N NO:

0 G v Q H the steps which comprise coupling diazotized 4c-aminodiphenylsulphide-t@oxamicacidwith meta-toluylenediamine and causing the intermediate compound thus formed to combine with diazotized dinitraniline.

6. New azo dyestuffs of the general formula wherein X represents the divalent residue of an intermediate coupling component, Z represents the coupled residue of an azo dye component and Y represents the residue of an oxamic acid derivative of the formula wherein n represents 1 or 8, the said dyestuffs being characterized by yielding on reduction a 4-aminodiphenylsulphide-t'-oxamic acid of the formula oooHooi PO'm-ONH, H

in which n represents 1 or 3, a diamidated body of the formula X(NH and an amidatedbody of the formula Z(NH such dyestuffs dyeing wool, acetate rayon, viscose rayon and cotton.

7 New azo dyestuffs of the general formula wherein X represents the divalent residueof an intermediate coupling component and Z the residue of an azo dye component; which dyestuffs are characterized by yielding on reduction a 4 F-aminodiphenylsulphide oxamic acid'of the formula a diamidated body of the formula X(NH 2 and an amidated body of the formula Z (NI-I such dyestuffs dyeing wool and acetate rayon;

8. New azo dyestuffs of the probable formula V e I wherein R represents hydrogen or CH and Z represents the residue of a diazotized amino the said dyestufis being characterized by I ooonooay-OS-O-mn I H V I body; thesaid dyes being characterized by yielding on reduction an oxamic acid derivative of the formula where R is hydrogen or CH and an amidated body Z(NI-I such dyestuffs dyeing wool, acetate rayon, viscose rayon and cotton.

9. The new azo dyestufit which may be representedby the probable formula yielding on reduction 4-amino-diphenylsul-, phide-4-oxamic acid 2: 3 4: 5 -tetraminotoluene and 1:2:4:-triaminobenzene and dyeing acetate rayon reddish brown shades.

10. The new azo dyestuffs which can be represented by the probable formula NH: COOHGQE-OSO-bkN wherein Z represents the coupled residue of a diazotized coupling component selected from a group comprising p-chloroaniline and p-nitroaniline. V

11. The new azo dyestufi' which can be represented by the probable formula wherein Z represents the coupled residue of u diazotized p-chloroaniline.

In testimony whereof I affix my signature.

' RAINALD BRIGHTMAN. 

